Organic Compounds : Shapes and Structures

 First synthesized organic compound was urea, which is prepared from an inorganic compound,
ammonium cyanate (by Wohler).

 Shape of carbon compounds

o sp orbital has 50% ‘s’ character. Thus, a sp hybridized carbon is more electronegative
than that possessing sp2 (33% s character) or sp3 (25% s-character).

 Hybridisation influences the bond length and bond enthalpy.

Some Characteristic Features of π-Bonds

 Parallel orientation of two p-orbitals on adjacent atoms is necessary for a proper sideways
overlap to form π-bond.
 Rotation about C = C double bond is restricted.

 Electron charge cloud of π-bond is located above and below the plane of bonding atoms.

 Electrons are easily available to attacking reagents.

Structural Representations of Organic Compounds

 Complete Structural Formula
Examples:

 Condensed Structural Formula

(Structural formula obtained by omitting some or all of the dashes representing covalent
bonds and then using a subscript to indicate the number of identical groups attached to an
atom)

 Bond-Line Structural Formula

o Only lines are used to represent the structure of organic compound.

o Carbon and hydrogen atoms are not shown.

o Lines representing the C − C bonds are drawn in a zig-zag fashion.

o For example − bone-line formula of 2,3-dimethylhexane can be represented as

o In cyclic compounds,
Classification of Organic Compounds

(I) Acyclic or open chain compounds consist of straight or branched chain compounds.

(II) Alicyclic or closed chain or ring compounds contain carbon atoms joined in the form of ring
(homocyclic). In some rings (heterocyclic), atoms other than carbon are present.
Aromatic Compounds

 Benzenoid aromatic compounds (include benzene and other related compounds)

 Non-benzenoid compounds (do not contain benzene ring)

 Heterocyclic aromatic compounds

Functional Group

 An atom or group of atoms joined in a specific manner which is responsible for the
characteristic chemical properties of the organic compound

Examples: Hydroxyl group (− OH), carboxylic acid group (− COOH), ketone group ,
etc.

Homologous Series

 A group or a series of organic compounds each containing a characteristic functional group

 The members of the series are called homologues.

 Successive members differ from each other in molecular formula by a −CH 2 unit.
  Alkanes, alkenes, alkynes, alkanoic acids, amines, etc. represent homologous series.

IUPAC (International Union of Pure and Applied Chemistry) System of

Nomenclature of Organic Compounds
 An organic compound can be named by identifying the parent hydrocarbon and the functional
groups attached to it.

 Using prefixes and suffixes, the parent name can be modified to obtain actual name.

IUPAC Name of Alkanes

 For straight chain hydrocarbons

Prefix →indicates the number of carbon atoms (except from CH 4to C4H10)

Suffix →‘ane’

 Branched chain hydrocarbons

Rules for the Nomenclature of Branched Chain Alkanes

 Longest chain in the molecule is identified (called parent or root chain).

 Numbering is done is such a way that the branched carbon atoms get the lowest possible
numbers.

 The names of alkyl groups attached as a branch are then used as prefix in the name of parent
chain. The position of the substituents is indicated by the appropriate numbers.

 If two or more identical groups are present, then prefix di (for 2), tri (for 3), tetra (for 4) are used.

 Numbers are separated by commas.

 Lower number is given to the one coming first in the alphabetical listing.
  Carbon atom of the branch that attaches to the root alkane is numbered 1.

Nomenclature of Cyclic Compounds/ Cyclic Alkanes

 They are named by prefixing ‘cyclo’ to the corresponding straight chain alkane.

Nomenclature of the Organic Compounds Having Functional Groups

 Parent chain of carbon atoms containing functional group is numbered in such a way that the
functional group is attached at the carbon atom possessing lowest possible number in the chain.
 The decreasing order of priority for the functional groups is

 The given table lists some functional groups and classes of organic compounds.

Class of Functional group IUPAC group IUPAC group

compounds structure prefix suffix

Alkanes − − - ane

Alkenes >C = C< − -ene

 Alkynes − -yne

Arenes − − −

Halides -X (X = F, Cl, Br, I) halo −

Alcohols −OH hydroxy -ol

Aldehydes −CHO Formyl or oxo -al

Ketones >C = O Oxo -one

Nitriles -C ≡ N cyano nitrile

Ethers -R-O-R- Alkoxy −

Carboxylic acids -COOH carboxy -oic acid

Carboxylate ions -COO− − −oate

Esters -COOR alkoxycarbonyl -oate

-COX
Acyl halides halocarbonyl -oyl halide
(X = F, Cl, Br, I)

Amines −NH2, >NH, >N- amino- −amine

-CONH2, CONHR,
Amides -carbamoyl -amide
-CONR2

Nitro compounds -NO2 Nitro −

 Examples

IUPAC name − 4-Methylheptan-3-ol

IUPAC name − 3-Oxopentanoic acid

IUPAC name − Hexa −1,3-dien-5-yne

Nomenclature of Substituted Benzene Compounds

 The substituent is placed as prefix to the word benzene.

 When the benzene ring is di-substituted,

 Substituent of the base compound is assigned number 1. The substituents appear in the name in
alphabetical order. Then the other substituents are numbered in the direction in which the next
substituent gets the lowest number.
  In some cases, common name of benzene derivatives is taken as the base compounds.

Isomerism in Organic Compounds & Reaction Mechanism

Isomerism
Two or more compounds having the same molecular formula, but different properties are called
isomers, and the phenomenon is called isomerism.

Structural Isomerism

 Compounds having the same molecular formula, but different structures are called structural
isomers.
 Chain isomerism:

o Two or more compounds having the same molecular formula, but different carbon
skeletons are referred to as chain isomers, and the phenomenon is called chain
isomerism.

o Example −

 Position isomerism:

o Two or more compounds differing in the position of functional group on the carbon
skeleton are called position isomers, and the phenomenon is called position
isomerism.

o Example −

 Functional group isomerism:

 o Two or more compounds having the same molecular formula, but different functional
groups are called functional isomers and the phenomenon is called functional
isomerism.

o Example − propanone (ketone) and propanal (aldehyde); both have the same
molecular formula C3H6O, but different functional groups

Another example −

 Metamerism:

o Two or more compounds arising due to different alkyl chains on either side of the
functional group in a molecule are called metamers, and the phenomenon is called
metamerism.

o Example −

Both have the same molecular formula C4H10O, but have different alkyl chains on
either side of the functional group (ether).

Stereoisomerism

 Compounds having the same molecular formula and having the same constitution and
sequence of covalent bonds, but differing in relative positions of their atoms or groups in
space are called stereoisomers. The phenomenon is called stereoisomerism.
 It can be classified as geometrical and optical isomerism.

Fundamental Concepts in Organic Reactions

Fission of a Covalent Bond

 Heterolytic fission: Bond breaks in such a way that the shared pair of electrons remains with
one of the fragments

o A carbocation is the species having a carbon atom possessing sextet of electrons and a
positive charge.

o Carbocations are classified as primary, secondary and tertiary.

o Example:

Primary carbocation − (ethyl cation)

Secondary carbocation − isopropyl cation,

Tertiary carbocation − tert-butyl cation,

o The order of carbocation stability is,

o The positively charged carbocation is sp2 hybridised. Thus, the carbocations have
trigonal shape.

o Carbocations are highly unstable and reactive species.

o Due to inductive and hyperconjugation effects, the alkyl groups directly attached to
the positively charged carbon stabilise the carbocations.

o The shape of methyl carbocation is as follows:

 Heterolytic cleavage can also give a species in which the carbon gets the shared pair (called
carbanion).
 o Carbanion is a carbon species carrying a negative charge on the carbon atom.

o It is an unstable and reactive species.

o The negatively charged carbanion is sp3 hybridised.

 Homolytic Cleavage:

o One of the electrons of the shared pair in a covalent bond goes with each of the
bonded atoms.

o The movement of the single electron takes place, instead of a pair of electrons.

o Homolytic cleavage can be represented as,

o Free radicals are the neutral species (atoms or groups) which contain an unpaired
electron. They can be classified as primary, secondary and tertiary.

o The order of stability of alkyl free radicals increases as,

o Reactions which proceed by homolytic fission are called free radical or homopolar or
non-polar reactions.

Nucleophiles and Electrophiles

 A nucleophile (Nu:) is a reagent that brings an electron pair, i.e., nucleus- seeking. Such a
reaction is called a nucleophilic reaction.

Example: Hydroxide (HO−), cyanide (CN−), carbanion

 An electrophile (E+) is a reagent that takes away an electron pair, i.e., electron- seeking. Such
a reaction is called an electrophilic reaction.

Example: Carbocation , neutral molecules having functional groups like carbonyl group
or alkyl halides
Electron Movement, Electron Displacement Effects in
Organic Compounds
Electron Movement in Organic Compounds

 Movement of electrons can be shown by curved arrow notation.

 Curved arrow shows how changes in bonding occur due to electronic redistribution during the
reaction.

 Curved arrow starts from the point from where an electron pair is shifted and ends at a
location to which the pair of electrons may move.

o From π bond to adjacent bond position

o From π bond to adjacent atom

o From atom to adjacent bond position

o For example,

Electron Displacement Effects in Covalent Bonds

 Inductive effect and resonance effects are the examples of permanent electron displacement
effects.
 Temporary electron displacement in a molecule when a reagent approaches to attack is called
electromeric effect or polarisability effect.

Inductive Effect

 In a covalent bond formed by the atoms of different electronegativity, the electron density
 moves towards the more electronegative atom of the bond.
 A shift of electron density results in a polar covalent bond.

o C − Cl is a polar covalent bond.

o (delta) represents fractional electronic charge.

o ( +
) represents some positive charge and ( −
) represents some negative charge.

o The arrow pointing from +

from −
represents the shift of electron density.

 The polarisation of σ- bond caused by the polarisation of adjacent σ- bond is called as the
inductive effect.

 Ability of the substituent(s) to either withdraw or donate electron density to the attached
carbon atom is related to inductive effect.

 On the basis of inductive effect, the substituent can be classified as electron-withdrawing or

electron donating groups relative to hydrogen.

 Electron withdrawing groups −−− Halogens, nitro (-NO 2), cyano (-CN), carboxy (-COOH),
ester (-COOR)

 Electron donating groups −−− Alkyl groups such as methyl (-CH 3) and ethyl (-C2H5)

Resonance Structure, Resonance Effect, Electromeric

Effect, and Hyperconjugation
 Benzene has a uniform C − C bond length of 139 pm [an intermediate value between C − C
single (154 pm) and C = C double (134 pm) bonds].
 It can be represented equally by energetically identical structures I and II.
  I and II are called resonance structures (canonical structures or contributing structures).

 Resonance structures are hypothetical. They individually do not represent any real molecule.

 They contribute to the stability of the compound.

 Some more examples of resonance:

 The energy of the actual structure (resonance hybrid) of the molecule is lower than that of any
of the canonical structures.

 Resonance energy is the difference in energy between the actual structure and the lowest
energy resonance structure.

 More the number of resonance structures, more is the resonance energy.

Resonance Effect (or Mesoamerica Effect)

 Defined as the ‘polarity produced in the molecule by the interaction of two π-bonds or between
a π-bond and lone pair of electrons present on an adjacent atom’
 Designated as R or M effect

 Positive Resonance Effect (+R Effect)

o Transfer of electrons is away from an atom or substituent group attached to the

conjugated system.
 o + R effect showing groups: − halogen, − OH, − OR, − OCOR, − NH 2, − NHR, − NR2, −
NHCOR

 Negative Resonance Effect (− R Effect)

o Transfer of electrons is towards the atom or substituent group attached to the

conjugated system.

o − R effect showing groups: − COOH, − CHO, , − CN, − NO2

Electromeric Effect

 Temporary effect
 Shown by the organic compounds having a multiple bond (a double or triple bond) in the
presence of an attacking reagent only

 Designated as E effect

 Defined as the complete transfer of a shared pair of π-electrons to one of the atoms joined by
multiple bonds on the demand of an attacking reagent

 Positive Electromeric Effect (+ E Effect)

o π- electrons of the multiple bonds are transferred to that atom to which reagent gets
attached.

o For example,

 Negative Electromeric Effect (− E Effect)

o π-electrons of the multiple bonds are transferred to that atom to which attacking
 reagent does not get attached.

o For example,

Hyperconjugation

 A permanent effect
 Involves the delocalisation of σ − electrons to C − H bond of an alkyl group directly attached
to an unsaturated system or to an atom with an unshared p-orbital (shown in figure)
Hyperconjugation in ethyl cation:

Hyperconjugation in propene:

 On the basis of hyperconjugation effect, the relative stability of carbocations is

o Greater the number of alkyl groups attached to a positively charged carbon atom,
greater is the hyperconjugation and stabilization of the cation.

 Hyperconjugation is also called no bond resonance.

Methods of Purification of Organic Compounds

Sublimation

 Used to separate sublimable compounds from non-sublimable compounds

 Principle: On heating, sublimable solid substances change from solid to vapour state without
passing liquid state.

Crystallisation

 Used for the purification of solid organic compounds

 Based on the difference in solubilities of the compound and impurities in the solvent

 The impure compound is dissolved in a solvent in which it is sparingly soluble at room

temperature, but appreciably soluble at higher temperature.

 The solution is concentrated to obtain a nearly saturated solution.

 On cooling the saturated solution, pure compound gets crystallised and is removed by
filtration.

Distillation

 Used to separate
o volatile liquids from non-volatile impurities

o liquids having sufficient differences in their boiling points

Example: separation of chloroform (b.p = 334 K) and aniline (b.p.= 457 K)

Distillation under Reduced Pressure

 Used to purify liquids having very high boiling points and those which decompose at or below
their boiling points
  Here, the liquids are made to boil at a temperature lower than their normal boiling points by
reducing the pressure on their surfaces. Liquid boils at the temperature at which vapour
pressure is equal to external pressure.

 Used to separate glycerol from spent-lye in soap industry

Fractional Distillation

 Used to separate the liquids of which the difference in boiling points is not too much
 Vapours of a liquid mixture are passed through a fractionating column (fitted over the mouth
of the round bottom flask) before condensation (shown in figure).

 This technique is used to separate different fractions of crude oil in petroleum industry.

Steam Distillation
  Used to separate substances which are steam volatile and are immiscible with water
 Steam volatile component is volatilised. The vapours get condensed in the condenser and are
collected as liquid in the conical flask.

 Used to separate aniline from aniline-water mixture

Differential Extraction

 An organic compound can be separated from its aqueous medium by shaking it with an
organic solvent in which it is more soluble than in water.

Chromatography

 Used to separate mixtures into their components, purify compounds, and also to test the
purity of compounds
 Two important classes − Adsorption chromatography and partition chromatography
Adsorption Chromatography

 Based on the fact that different compounds are adsorbed on an adsorbent to different degrees
 Commonly used adsorbents − Silica gel and alumina

 A mobile phase is allowed to move over a stationary phase (adsorbent). Then the components
of the mixture move by varying distance over the stationary phase.

 Two main types − Column chromatography and thin layer chromatography

 Column chromatography − This technique involves separation of a mixture over a column

of adsorbent (stationary phase) packed in a glass tube.

Most readily adsorbed gas (here ‘a’) is retained at the top and others (b and c) come down to various
distances in the column (shown in above figure).

 Thin layer chromatography − Involves separation of substances of a mixture over a thin

layer of an adsorbent coated on glass plate (shown in figure)
 Developed chromatogram:

o The relative adsorption of each component of the mixture i.e., retardation factor (or Rf
value) is given by,

Partition Chromatography

 Based on continuous differential partitioning of components of mixture between stationary and

mobile phases
 Paper chromatography is a type of partition chromatography.

 For paper chromatography, chromatography paper (a special type of paper) is used which
contains water trapped in it and acts as the stationary phase.

 The chromatography paper retains different components according to their differing partition
in the two phases.

 The developed paper is called chromatogram.

Qualitative Analysis of Compounds
Detection of Carbon and Hydrogen

 Detected by heating a compound with copper (II) oxide

 Carbon present in the compound gets oxidised to CO 2, which is then tested with lime water
(lime water turns milky)

 Hydrogen present in the compound is oxidised to water, which is then tested with anhydrous
copper sulphate (anhydrous copper sulphate turns blue)

Detection of Other Elements (N, S, P and Halogens)

Lassaigne’s Test

 Elements (N, S, P and halogens) present in the organic compound are converted from the
covalent form to the ionic form by fusing the reaction with Na metal.

 NaCN, Na2S and NaX, so formed, are extracted from the fused mass by boiling it with distilled
water. The extract obtained is known as sodium fusion extract.

 Test for Nitrogen (N)

o Sodium fusion extract is boiled with FeSO4.

o It is then acidified with sulphuric acid

 o Formation of Prussian blue colour confirms the presence of nitrogen.

 Test for Sulphur (S)

o Sodium fusion extract is acidified with acetic acid and lead acetate is added to it.

Formation of black precipitate of lead sulphide indicates the presence of sulphur.

o When sodium fusion extract is treated with sodium nitroprusside, violet colour
appears.

Appearance of violet colour indicates the presence of sulphur.

o When both N and S are present in an organic compound, sodium thiocyanate

(NaSCN) is formed.

NaSCN then gives blood red colour, and not Prussian blue, since there are no free
cyanide ions.

 Test for Halogens

o Sodium fusion extract is acidified with HNO3 and then treated with AgNO3.

o A white precipitate (soluble in ammonium hydroxide) indicates the presence of

chlorine.

o A yellowish precipitate (sparingly soluble in ammonium hydroxide) indicates the

presence of bromine.

o A yellow precipitate (insoluble in ammonium hydroxide) indicates the presence of

iodine.

 Test for Phosphorus

o Compound is heated with an oxidising agent (Sodium peroxide).

 o Phosphorus is then oxidised to phosphate.

o The solution of phosphate is then boiled with HNO 3 and then treated with ammonium
molybdate.

Quantitative Analysis : Carbon and Hydrogen; Nitrogen

Carbon and Hydrogen

 Organic compound of known mass is burnt in the presence of excess of oxygen and copper
(II) oxide

o Carbon and hydrogen (present in the compound) gets oxidised to CO 2 and water
respectively.

 The mass of water produced can be determined by passing the mixture through a weighed U-
tube containing anhydrous CaCl2.
  U-tube containing concentrated solution of KOH absorbs CO 2.

 The increase in the mass of CaCl2 and KOH gives the amounts of water and CO2, from which
the percentages of C and H can be calculated as follows:
Mass of the organic compound = m g
Mass of H2O = m1 g
Mass of CO2 = m2 g

∴Percentage of carbon =

And, percentage of hydrogen =

Nitrogen

 Dumas Method
o When heated with CuO in an atmosphere of CO 2, the nitrogen-containing organic
compound yields free nitrogen, CO2 and H2O.

o The mixture of produced N2 and CO2 gases is collected over an aqueous solution of
KOH so that CO2 is absorbed by it.

o Nitrogen gas is collected in the upper part of the graduated tube.

Mass of the organic compound = m g
Volume of nitrogen collected = V1 mL
Room temperature = T1K

Volume of nitrogen at STP =

 = V mL (Suppose)
Where,
p1 = Pressure of nitrogen
V1 = Volume of nitrogen
p1 = Atmospheric pressure − Aqueous tension
22400 mL N2 at STP weighs 28g.

V mL N2 at STP weigh = g

∴Percentage of nitrogen

 Kjeldahl’s method

o Compound containing nitrogen is heated with conc.H 2SO4.

o Nitrogen gets converted into (NH4)2SO4.

o Resulting acidic mixture is heated with an excess of NaOH.

o The liberated NH3 gas is absorbed in an excess of a standard solution of H 2SO4.

o Amount of NH3 produced is determined by estimating the amount of H 2SO4 consumed

in the reaction, which is calculated by subtracting the un-reacted amount of H 2SO4
from its total amount.

o Calculations:
Mass of the organic compound = m g
Volume of H2SO4 of molarity M taken = V mL
Volume of NaOH of molarity M used for titration of excess of H2SO4 = V1 mL
V1 mL of NaOH of molarity M

mL of H2SO4 of molarity M

Volume of H2SO4 of molarity M unused = mL

mL of H2SO4 of molarity M
 =2 mL of NH3 solution of molarity M
1000 mL of 1 M NH3 solution contains 17g NH3 or 14g of N.

mL of NH3 solution of molarity M contains

g of N.

∴Percentage of N

o This method is not applicable to the compounds containing nitrogen in nitro and azo
groups; and to the nitrogen-containing ring (pyridine). This is because the nitrogen
present in these compounds does not change to (NH 4)2SO4 under these conditions.

Quantitative Analysis: Halogens, Sulphur, Phosphorus and

Oxygen
Halogens (Carius Method)

 An organic compound (of known mass) is heated with fuming HNO 3 in the presence of AgNO3
(contained in a Carius tube) in a furnace. (shown in the figure)
  Halogens present in the compound form the corresponding silver halide (AgX).

 AgX is filtered, washed, dried and weighed.

 Calculations:
Mass of the organic compound = m g
Mass of AgX formed = m1g
1 mol of AgX contains 1 mol of ‘X’

Mass of halogen in m1 g of AgX

Percentage of halogen

Sulphur

 An organic compound (of known mass) is heated in a Carius tube with sodium peroxide or
fuming HNO3.
 Sulphur present in the compound gets oxidised to H 2SO4, and it gets precipitated as BaSO4 by
adding excess of BaCl2 solution in water.

 The precipitate is filtered, washed, dried and weighed.

 Calculations:
Mass of the organic compound taken = m g
Mass of the barium sulphate formed = m1g
1 mole of BaSO4 = 233 g of BaSO4 = 32 g of sulphur

m1g of BaSO4 contains g of sulphur.

 Percentage of sulphur

Phosphorus

 An organic compound (of known mass) is heated with fuming HNO 3.

 Phosphorus present in the compound is oxidised to phosphoric acid, which is precipitated as
ammonium phosphomolybdate, (NH4)3PO4.12 MoO3 [by adding NH3 and ammonium
molybdate].

 Calculations:
Mass of the organic compound taken = m g
Mass of (NH4)3 PO4.12 MoO3 = m1g
Molar mass of (NH4)3 PO4.12 MoO3 = 1877 g

Percentage of phosphorus

Oxygen

 Usually estimated (in terms of percentage) by the difference between the total percentage-
composition (100) and the sum of the percentages of all other elements.
 Can be estimated directly as well: If an organic compound (of known mass) is heated in a
stream of N2 gas, it gets decomposed to form O2 gas and other gaseous products.

o Two moles of CO2 are obtained from one mole of O2, i.e., 88 g of CO2 is obtained if 32
g of O2 is liberated.

o Calculations:
Mass of the organic compound = m g
Mass of CO2 produced = m1g

∴m1 g of CO2 is obtained from

∴Percentage of O2